We report a 1,3-heteroaryl acyloxylation of 3-substituted propargylic esters with readily available heteroarenes, including indoles, pyrroles, furans and thiophenes, under palladium catalysis. Heteroaryl-functionalized Z-enol ester products were obtained in a single step with complete levels of γ-regioselectivity and anti-hydroacyloxylation stereo-control. The use of the palladium-tri(2-furyl)phosphine complex in polyfluorinated alcoholic solvents was shown to be crucial to the reactivity of the desired pathway based on control experiments. High atom economy, mild conditions (30 °C) and broad tolerance to functional groups make this protocol attractive. Finally, the synthetic utility of this method was demonstrated by gram-scale synthesis and downstream derivatizations of the product.

中文翻译：

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钯 (II) 催化的炔丙基亲电子试剂的 1,3-杂芳基酰氧基化


我们报道了在钯催化下，3-取代的炔丙酯与容易获得的杂芳烃（包括吲哚、吡咯、呋喃和噻吩）发生1,3-杂芳基酰氧基化。一步获得杂芳基官能化的 Z-烯醇酯产物，具有完全的 γ-区域选择性和抗加氢酰氧基化立体控制水平。根据对照实验，在多氟醇溶剂中使用钯-三（2-呋喃基）膦络合物对于所需途径的反应性至关重要。高原子经济性、温和的条件（30°C）和对官能团的广泛耐受性使该协议具有吸引力。最后，通过产品的克级合成和下游衍生化证明了该方法的合成效用。